Contact method of sulphuric acid manufacture



l. HECHENBLEIKNER CONTACT METHOD OF SULPHURIC ACID MANUFACTURE April 21, 1936.

Filed Nov. 17, 1931 mmJOOU om Gamin INVENTOR WGENLMN HECHENBLEIKNER BY l ATTO R N EYS Patented Apr. 2l, 1936 UNITED STATES CONTACT METHOD 0F SULPHURIC ACID MANUFACTURE Ingenuin Hechenbleikner, Charlotte, vN. C., assignor to Chemical Construction Corporation, Charlotte, N. C., a corporation of Delaware Application November 17, 1931, Serial No. 575,549

4 Claims.

:This invention relates to sulphuric acid manufacture, and has special reference to theprovision of an improved contact method of making sulphuric acid.

In contact methods of suphuric acid manufacture, sulphur or pyrites or zinc sulphide ore v is burned in the presence of air or oxygen in a burner or furnace Where a mixture of SO2 gas and air is produced, which mixture is then passed to a catalyti'c converter wherein the SO2l gas is converted to sulphuric anhydride. The sulphuric anhydride is then passed through absorption apparatus where the final sulphuric acid product is obtained.

In the practice of this contact method of making sulphuric acid, it has long been known that the SO2 gases generated in the burner or furnace must be purified to prevent the impurities therein from poisoning the contact or catalytic mass of the converter; and one of the chief problems has been to remove S03 mist which is formed and which isl present in considerable amounts in the burner gas. In the old cold purification processes, it was necessary to cool the generated gases to approximately atmospheric temperature, remove moisture and iilter out this S03 mist by means of large and expensive coke or mineral wool filters. It was necessary to completely remove this mist in orderto prevent the poisoning of platinum catalyst then generally in use as well as to prevent the corrosion of the apparatus. Since brimstone has come into general use, and due to its great purity, the elaborate cold purification methods have become unnecessary, and yet the air used for burning the brimstone has to be dried to remove moisture and the temperature of the gases between the sulphur burner and the converter must be maintained at a point high enough (above the dew or condensation point of sulphuric acid) so aS to prevent the formation of sulphuric acid mist.

- I have discovered that sulphuric acidrmay be manufactured by producing an SO2 gas substantially Without the concomitant formation of S03, which SO2 gas may then be converted catalytically to sulphuric anhydride. By substantially inhibiting the formation of S03, the tendency to or liability of formation of sulphuric acid mist is avoided. TheY SO2 gas may thereby be generated without regard to the problem of moisture content thereof, the subsequent treatment of the SO2 gas is thereby facilitated and the problem of catalyst kpoisoning by S03 mist is eliminated. This improved contact process `of sulphuric acid manufacture comprises a prime object of my present invention.

In the practice of the invention exemplified herein, the SO2 gas is produced from a sulphur containing body such as acid sludge obtained in the rening of petroleum, tar and other organic materials. I have found that acid sludge (which may contain sulphuric acid, sulphonic acids, sulphates, acidtars and other organic hydrocarbons) may be controllably reacted in a retort to produce SO2 gas of relatively high concentration,`as for example from 8 to 14% SO2, and substantially free from either solid or vapor impurities, the gases produced consisting of S03 substantialy free from tarry vapors, HzS gas, S03, S and sulphuric acid vapors and containing only water in the form of steam and a minimum amount of light hydrocarbons which may be removed with little difficulty. I have furthermore found that the produced gases, after the removal of Water and the small amount of light hydrocarbons, may readily be admixed with oxygen in the form of air and dried and may then be efliciently converted to sulphuric anhydride in a catalytic converter, preferably of the vanadium catalyst type, wherein a very high conversion yield of from 97 to 98% may be obtained. The provision of this improved method for the generation of SO2 gas from acid sludge and the eilicient conversion thereof to sulphuric anhydride is Va'further prime object of my present invention.

To the accomplishment of these objects 'and such ancillary objects as will hereinafter appear, my invention consists in the processes and steps ofV thev processes hereinafter more particularly described and sought to be defined in the claims, reference being had to the accompanying drawing which shows a diagrammatic layout of the plant employed in the practice of the present process.

Referring now more in detail to the drawing, the process of my inventionr consists generally in producing SO2 gas in a gas generator I 0, which gas is laden with moisture, in flowing the thus generated gas through a condenser 26, in then admixing oxygen or air with the gas as at 32, in then flowing the mixture of SO2 gas and oxygen through a dehydrator 33, thence through an S03 converter 39, and thereafter through an absorber 40 wherein the product acid is obtained.

In the gas generator ID" the SO2 gas is pro-` duced in an atmosphere low in free oxygen, the

oxygen content of the gas atmosphere being less than 10% by volume, the gases entering the gas generator having preferably an oxygen content of from 2 to 6%. In thisV gas generator SO2 gas is produced substantially without any aocompanying sulphuric acid or anhydride distillation. In the condenser 26, moisture in the gases is lcondensed and removed from the system and here any small traces of S03 if formed may be condensed and removed. vThe amount of air introduced at 32 is such that the ratio of oxygen to SO2 gas entering subsequently into the converter 39 is o f the order of 1.4 to 1. The SO2 gas leaving the condenser 26 is substantially at room temperature (generally about 100 F.) and therefore contains moisture; and the dehydrator 33 functions to dehydrate the mixture. of this gas with the air or oxygen.

In the more specific embodiment of the invention, the S02 gas is generated from acid sludge and the gas generator l0 is therefore designed especially for the treatment of acid sludge. This generator preferably comprises a rotary cylinder or drum made of iron or steel preferably interiorly subdivided by means of one or more annular members such as I3 into a plurality of separate and intercommunicating compartments. This drum retort is provided at its opposite ends with reduced cylinder sections I4 and I5 respectively which serve for the ingress and egress of the reacting constituents and resulting products for the retort. The construction and design of this retort may be Varied within substantial limits and for a small plant such for example as a plant of two sludge ton daily capacity this retort may have an inside length of from 8 to 10 feet and an inside diameter of 2 feet. The rotational speed imparted to this retort may be of the order of 16 R. P. M.

The cylindrical end section I4 of the retort is made to serve as the intake end for combustion gases produced in a furnace B with which is associated a furnace blower 25, and the opposite cylindrical end section I5 of the retort is made to serve as the exit or expulsion end for S02 gases produced in the retort or gas generator. Where the gas generator is employed for the treatment of acid sludge, the gas exit end I5 thereof is also made to serve as the inlet end for the acid sludge, the sludge being introduced into the retort itl through a feed pipe 22', and the opposite end I fi is made to serve as theexpulsion end for the carbonaceous residue of the sludge, the carbonaceous residue being removed from the system through a hopper 2|', which hopper is sealed at its bottom by means of a slide dooror the like. Since the retort or gas generator l0 is rotatable, the joints between the retort and the combustion furnace B' at one end and those between the retort and the gas outlet head 23 at the other end are suitably packed with some stuffing material. It is highly desirable to make these joints air-tight so as to prevent ingress of atmospheric air into the retort at either end or the loss of gases from the retort.

The. gas generator and the process of generating the S02 gas therein are more specifically set forth and claimed in my copending applications Serial Nos. 568,051 and 568,050, now Patent No, 1,953,225, dated April 3, 1934, both led Oct. 10, 1-931.

The combustion gases employed may be obtained from a variety of sources and may be produced for example from the burning of oil, powdered coal, coke or other heat producing materials, and may also be produced from natural gas. The combustion gases may also be obtained by burning sulphur or hydrogen sulphide or similar sulphur containing compounds or products. The combustion gases provide an atmosphere in the retort or gas generator which aids in producing rapid as well as complete reduction and conversionof the sulphur containing compounds in the sludge to S02. I have found, however, that the free oxygen content in the reaction atmosphere. in the retort should be of an amount insuilicient to complete the subsequent sulphuric acid contact reaction, and I have empirically determined that the combustion gases should contain an oxygen content below 10% by volume and preferably between 2 to 6%. I have found that the control of the oxygen content or proportion in the combustion gases and in the reaction atmosphere of the retort is important in producing a number of advantageous results. The presence of free oxygen is, I believe, a factor in inhibiting the formation of H2S gas in the retort when it is operated at the critical temperature range, and is also a factor in effecting complete combustion of the furnace gases; and the maintenance of the low proportion of free oxygen is, I believe, a factor in giving rise to a reaction atmosphere in the retort wherein the desired reduction and conversion of the sulphur containing compounds to SO2 is effected. Alsol With a low oxygen content danger of res is obviated and oxidation of the hydrocarbons in the acid sludge is minimized. The copious evolution of the produced S02 gas in or about the middle section of the retort in all probability provides a protective blanket between' the combustion gases and the lighter hydrocarbons distilled off in the gas exit end of the retort.

The production of an S0?J gas substantially without the concomitant generation of S03 is of especial importance in the practice of my present' invention. The operation of the gas generator is so predetermined and practiced that the S02 gas is generated substantially without any accompanying sulphuric acid or anhydride distillation and substantially without any conversion in the retort of SO2 to S03. By means of my present process, the sludge body is gradually brought up to the higher temperatures, the gradual heating being a factor in avoiding such rapid heating or local overheating as causes a distillation of S03. The avoidance of the formation of S03 at any stage of the process is very important, as aforesaid, since such S03 formation results in the creation of the acid mist which is a colloidal fume and which passes through the condenser, the converter and the absorber (in the subsequent apparatus) and out into the atmosphere and creates a great nuisance. Moreover, as above set forth, this S03 mist acts as a poison for the contact mass. I have found that the avoidance of S03 distillation is the result of a combination of reasons, comprising mainly first the fact that at the gas exit end of the retort the temperatures are too low for the distillation of S03, second, the fact that the range of reacting temperatures in the retort is suitably governed, l and third, the fact that the rateo-f bringing. up`

the sludge to the reaction temperatures is so controlled and gradual that the formation of S03 isv inhibited, or if any is produced, it is reacted with the hydrocarbons to produce the reduction thereof to S02 so that ultimately no S03 accompanies the exit gases. The restriction of the free oxygen content in the retort is, I believe, also a factor in avoiding conversionof S02 to S03 in the retort.

For obtaining a preferred temperature and reaction control, the combustion gases may have entering temperatures Varying from 1500 to 2500 F., and exiting temperatures of 240 to 260 F., while the temperature ranges for the sludge body in the retort when treating say a blended liquid sludge may be from 212 to 300 F. at the gas exit end of the retort, from 300 to 400 F. in the central zone of the retort, and from 400 to 420 F.at the gas entrant end of the retort.

The producedy gasescontaining SO2 and laden with moisture discharging yfrom the retort and exiting at the vgas outlet 23 are first led through the condenser 26 which may be cooled by water entering through the pipe 21 and passing out through the pipe 23. In .this condenser the water and the small amount of oil present-in the exit gases are condensed, and these separating into stratied layers are readily withdrawn into the! `water and oil boots-29 and 30. Here also may be removed any small traces of S03 if any are formed. It will be understood that if asubstantial'quantity of sulphuric acid mist were produoedor formed prior to the condenser 26, the condenser would be inadequate to remove or scrub the same from the gases. The condenser serves also to cool the gases to a low temperature which is substantially room temperature and which more specifically is about 100 F. If desired, in order to prevent an undue rise in the pressure in the plant or system, a pressure relief valve such as 3| may be employed following the condenser 26. Y j

. ,The remainder of the plant apparatus illustrated in the drawing is intended for the subsequent conversion of SO2 to sulphuric anhydride and sulphuric acid. The oxygen content of the SO2 gas leaving the condenser being insufcient for the subsequent conversion step, oxygen or air is introduced as aforesaid at 32 into the gas line. I have found that to obtain a desired 97 to 98% conversion in a converter employing a vanadium compound contact mass, that for reasons hereinafter discussed, .the ratio of oxygen to SO2 entering the converter should be of the order of 1.4 to 1,V the oxygen content being preferably between the limits of 1.3 to 1.6, 1.4 being the optimum Value. Accordingly, at 32 suflicient air is added to the gases (already containing some oxygen) to produce the desired oxygen to SO2 ratio. As shown, the air is preferably added in advance of the dehydrator 33 and after the cooler-condenserV 26. By adding the air at this point, the volume of gas passing through the condenser is reduced, thus reducing the size of the condenser required; furthermore, if the air were added inA advance of the condenser, all of the gases exiting from the condenser would be saturated with moisture and the dehydrating problem would be4 aggravated. By adding the air after the cooler and in advance of the dehydrator, the added air is only partly saturated with moisture and the load on the dehydrating tower is relieved. The

air need not be pre-dried, the dehydrator being relied upon to dry the air as well as the SO2 gas.

The dehydrator or drying tower 33 through which the mixture of air'and SO2 gas is passed is supplied with a stream of sulphuric acid moving countercurrent to the gas iiow under the action of an acid'pump 34 and circulating in the pipe system a, the sulphuric acid serving the purpose -of drying the air and gas mixture. This mixture then passes through an orice meter'35 into and through the blower 36 which acts in conjunction with the blower 25 of the furnace to cause or induce the gas flow through the system. From the blower the gas mixture is delivered to a heat exchanger 31 which functions to reheat the gases, preheating the same for the purpose of bringing them up to suitable conversion temperatures. It will be understood that the gases having passed throughk the condenser and drying tower have been cooled to a temperature below the catalytic conversion temperature and therefore require reheating.

The air and SO2 gas mixture passes from the heat exchanger 31 through the pipe 38 into a catalytic converter 39. In the preferred practice of the present process this converter is of the vanadium type, Vthe contact mass comprising vanadium compounds of any of a numberrof well known kinds. A vanadium catalyst is preferred, since it is not aiTected by such gaseous platinum contact mass poisons as chlorine and arsenic. I have discovered that with the use of Vanadium Contact mass it is highly desirable to maintain a ratio of oxygen to SO2 entering the converter of the order ofl.4 to l in order to obtain the desired 97lto 98% conversion ordinarily obtained in commercial plants an-d without the use of an excessive amount of contact material. Since small traces of hydrocarbons may be found in the gases entering the converter, and `since these require oxygen for their oxidation, sufficient oxygen should be added to the gases at 32 so that the ratio of 1.4 to 1 is maintained in the converter after the oxidation of such compounds. I have found that both the equilibrium and the velocity of reaction are afectedby the-oxygen to SO2 ratio. The action of the vanadium contact mass is no doubt due to the different stages of oxidation of the Vanadium compounds. With a oertain ratio of oxygen to SO2 there will be established a certain ratio between the'high stage oxidized vanadium compound and the low stage. In case the ratio of oxygen to SO2 is reduced, it follows that a reduction of the vanadium compounds will also take place, forming one inactive part of the catalyst. Due to the retarding'iniiuence on. the reaction caused by the lower content of oxygen, a larger amount of contact mass is required for getting the samel conversion; whereas a decrease of the oxygen content in the gas reduces the active part of the catalyst. Thus a lowering of the oxygen content produces a reduction in the reaction of the Vanadium mass. Where a low oxygen ratio is used, I have found the result lto be that the hotspot in the converter moves further away from the gas entrant end, indicating a building up of inactive Contact mass and the conversion at-the same time further decreases rapidly, indicating inactivity of `the mass. I have found that the optimum results, as aforesaid, are produced with an oxygen factor of from 1.3 to 1.6, the optimum ratio being, as indicated, 1.4 to 1. Although a larger oxygen content may be used, this of course is undesirable, since this increases the volume of gas to be treated, requiring larger converters and absorbers, etc.

The converted gases (S03) discharging from the converter 33 are led into the absorption tower 40, and if desired a part of these gases may be bypassed through the pipes 4l and i2 into and through the heat exchanger 3l' for the purpose of supplying the heating medium for the heat .exchanger, and conversely for the purpose of cooling the S03 gases to the desired absorption temperatures. The cooled S03 gas then returns through the pipe 3 to the pipe i4 leading to the absorption tower 133. In the absorption tower' 40 the converted S03 gas is absorbed in the usual manner by means of acid which is supplied by a pump t5 and-circulates through the pipe system b. 'I he sulphuric acid produced in the absorption tower is led therefrom into the cooler 46.

In starting up; the converter apparatus, a starting up furnace 4l may be utilized, this starting up furnace functioning to supply hot products of combustion to the heat exchanger 31 through the pipe 42; and at such time the valve 48 in the rpipe line 4| is closed. Until the heat exchanger acquires the desired temperature, these combustion products may be vented through the outlet 48 to atmosphere.

The contact sulphuric acid system of the process may be self-contained in the supply of sulphuric acid for the absorber 40 and for the dehydrator 33. To accomplish this some of the product acid of the system obtained in the absorption apparatus 40 is circulated to the dehydrator 33 and serves as the make-up acid therefor, and conversely, the diluted sulphuric acid of the dehydrator 33 is returned to the absorber 40 and serves as supply for the makeup acid for the absorber. Accordingly the pipe system a of the dehydrator 33 and the pipe system b of the absorber 40 are interconnected by a pipe system c through which the product acid is delivered to the dehydrator controlled by means of a valve 50 and a pipe system d through which the drying or dehydrating acid is delivered from the dehydrator back to the absorber, the flow of the latter being controlled by means of a valve 5|. The acid circulating in the absorber 40 may be a 98% acid and that circulating in the dehydrator 33 may be a 66 Baum acid. Where high strength acid such as 20% or higher oleum is desired, water may -be abstracted from the system by returning a part of the dehydrating acid to the gas generator I0 through the pipe line e controlled by means of a valve 52, all as more specifically described and claimed in my companion application to Process of making concentrated sulphuric acid or oleum, Serial No.

574,244, filed November 11, 1931.

The practice of my improved process and the operation of the plant will in the main be fully apparent from the above detailed description thereof. The S02 gas may be generated without regard to the problem of moisture content thereof; and although moisture may be present in large amounts in the produced gases, the gases may be obtained at relatively low temperatures, and may be further cooled to atmospheric temperatures and therefore below the dew or condensation point of sulphuric acid without the liability or danger of fo-rming sulphuric acid mist. The substantial absence of any formation of S03 in the gas generator renders unnecessary the use of the complicated treatment and apparatus of the cold purication process, although the gases issuing from the gas generator and subsequently treated are handled at low temperatures. With the process of the invention, substantially the only treatment of the gases required prior to the converter stage is to run the gases through the relatively small condenser 26 and to then dehydrate the gases along with the air admixed therewith. The air itself need not be pre-dried. By means of the process, moreover, catalytic conversion with vanadium contact mass is very eiciently accomplished.

While I have shown the process employed with acid sludge, of which different varieties may be used, such as liquid sludges and sludges of the more viscous and solid types, it will be understood that other sulphur containing bodies may be used instead. It will also be understood that the process may be employed for the concentration of any weak sulphuric acid or for the treatment of a byproduct sulphuric acid such as a Weak sulphuric acid resulting from the pickling of steel. Heretofore acids of this type have been of little value, the strength of the acid being too low'to permit of economical concentration. Such acids may be treated in my process by adding to them a reducing agent such as hydrocarbon oils. It Will be further understood that while I prefer toVV embody all of the principles of the invention in the apparatus and process as described, the process may be widely varied to employ any one or a number of these principles in combination to effect `any one or a number of the advantages fiowing therefrom, all as I have attempted to define in the following claims.

I claim:

1.l The process of producing sulphuric acid which consists in flowing heated gases over an acid sludge from the sulphuric acid purification of hydrocarbonaceous material to effect a reaction of the sludge with a consequent reduction of the sulphuric acid content or compounds thereof to SO2 gas, the said heated gases cohtaining a proportion of vfree oxygen of about 2 to 6%, theoxygen content being substantially less than that required for subsequent catalytic conversion of the SO2 gas, in thereafter admixing the produced SO2 gas with a further supply of oxygen, and in then converting the S02 and oxygen mixture to sulphuric anhydride.

2. The process of producing sulphuric acid which consists in fiowing heated gases over an acid sludge from the sulphuric acid purification of hydrocarbonaceous material to effect a reaction of the sludge with a consequent reduction of the sulphuric acid content or compounds thereof to S02 gas, theY said heated gases containing a proportion of free oxygen of about 2 to 6%, the said proportion of free oxygen being substantially less than that required for subsequent catalytic conversion of the SO2 gas.

3. A method of producing sulphuric acid by the contact'process which comprises subjecting acid sludge from the sulphuric acid purification of hyd'rccarbonaceous material to a heat treatment toA produce S02 without distillation of S03, the treatment taking place in the presence of sufficient oxygen to prevent the presence in the S02 gas evolved of H2S but insufficient to effect conversion o-f the SO2 to S03, cooling the gas to condensel out moisture, admixing an amount of oxygen suflicient for the conversion of the S02 to S03, dehydrating the gas mixture and passing the mixture at reaction temperature over a contact sulphuric acid catalyst.

4. A method of producing sulphuric acid by the contact process which consists in subjecting a body containing S04 compounds and carbonaceous reducing agents, the mixture also including combustible hydrogen containing compounds, to a heat treatment to effect reduction to S02 in the presence of suicient oxygen to prevent formationof vI-IzS but insufficient to permit of conversion ofthe S02 formed to S03, maintaining the reaction conditions such as to substantially prevent distillation of S03, cooling the gas to a low temperature sufcient to condense out Water, admixing with suicient oxygen to permit conversion of the S02, dehydrating the mixture and passing the dehydrated gas at reaction temperature over a contact sulphuric acid catalyst.

INGENUIN HECHENBLEIKNER. 

